A refinement of everyday thinking: the energetic span model for kinetic assessment of catalytic cycles

被引：220
作者：
Kozuch, Sebastian [1 ]
机构：
[1] Weizmann Inst Sci, Dept Organ Chem, Rehovot, Israel
来源：
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE | 2012年 / 2卷 / 05期
关键词：
D O I：
10.1002/wcms.1100
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The energetic span model is a bridge connecting the kinetic outcome of experimental and theoretical catalysis. It proves the utility of working with Gibbs energies (E-representation) instead of the rate constants (k-representation), in line with the assertion saying that there are no rate-determining steps, but rate-determining states. With this model the turnover frequency (TOF), turnover number (TON) and the kinetic determining factors can be obtained from the reaction profile of a computed catalytic cycle. In this way, it is possible to examine, explain, and predict the efficiency of a catalyst. The effect of concentrations, different pathways, preactivation and deactivation, and the comparison of catalysts and reactants are analyzed with several examples from the literature. In addition, the AUTOF program (excel version) is presented, allowing the fast and simple analysis of theoretically calculated catalytic reactions. (c) 2012 John Wiley & Sons, Ltd.
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收藏
页码：795 / 815
页数：21
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[61]  
Guihaume J., Halbert S., Eisenstein O., Perutz R.N., Hydrofluoroarylation of alkynes with Ni catalysts. C-H activation via ligand-to-ligand hydrogen transfer, an alternative to oxidative addition, Organometallics, 31, pp. 1300-1314, (2011)
[62]  
Kuriakose N., Kadam S., Vanka K., A theoretical study of metal-metal cooperativity in the homogeneous water gas shift reaction, Inorg Chem, 51, pp. 377-385, (2011)
[63]  
Garcia-Melchor M., Pacheco M.C., Najera C., Lledos A., Ujaque G., Mechanistic exploration of the Pd-catalyzed copper-free Sonogashira reaction, ACS Catal, pp. 135-144, (2011)
[64]  
Li Z., Jiang Y., Fu Y., Theoretical study on the mechanism of Ni-Catalyzed Alkyl-Alkyl Suzuki cross-coupling, Chem Eur J, (2011)
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